SURFACE CHEMISTRY
DEFINITION
Surface science is the study of chemical phenomena that occur at the interface
of two phases (solid–liquid interfaces, solid–gas interfaces, solid–vacuum
interfaces, and liquid-gas interfaces).
(or)
It is defined as the study of chemical reactions at interfaces.
BASICS
Surface chemistry is important in many critical chemical
processes, such as enzymatic reactions at biological interfaces
found in cell walls and membranes,
in electronics at the surfaces and interfaces of microchips used in
computers, and
the heterogeneous catalysts found in the catalytic converter
used for cleaning emissions in automobile exhausts.
T E R MI NO LO G I E S
DIFFERENCE BETWEEN ADSORPTION
AND ABSORPTION
TYPES OF ADSORPTION
ADSORPTION OF GASES ON SOLIDS
• The solid surface is adsorbent
• The gas adsorbed is adsorbate
• The extent of adsorption
depends on many factors.
FACTORS AFFECTING THE EXTENT
OF ADSORPTION
(i) Nature of Adsorbent
The adsorption depends on the type of adsorbents used. When the adsorbent is highly
porous the rate of adsorption increases. Activated carbon, metal oxides like aluminum oxide
silica gel and clay are commonly used adsorbents. The rate of adsorption can be increased
by activation process. It helps in enhancing the pores in the adsorbent
Eg. charcoal adsorbs 0.011 gms of CCl4 at 24°C and activated charcoal adsorbs 1.48 gm of at 24°C.
Activation of adsorbent
During activation, the adsorbent is heated in steam to about 1500°C. Heating drives out all
impurities and leads to a lager free surface for adsorption. It can be done in 3 given ways
• By making the surface of adsorbent rough.
• By heating the adsorbent in vacuum so that the water vapour present in pores leave those
pores.
• By increasing the surface area of adsorbent
(ii) Surface area of adsorbent
Increase in surface area of the adsorbent increases the adsorption of gases and the
extent of adsorption depends on two factors
• Greater the surface area greater the adsorption-Increase in surface area increases the
number of adsorbing sites.
• Larger the porosity greater the adsorption-Finely divided and highly porous materials
acts as good adsorbents.
Eg. Charcoal and silica gel (excellent adsorbents).
(iii) Nature of Gases
The amount of gas adsorbed by a solid depends on the nature of the gas. Easily
liquefiable gases like HI, NH3, CI2, SO2 etc., are adsorbed more easily then the
permanent gases like H2, N2, and O2 etc. Physical adsorption is non-specific in nature,
so any gas will be adsorbed on the surface under any given conditions of temperature
and pressure. Chemisorption is specific in nature so only those gases which forms
chemical bonds will be adsorbed.
The nature of gas depends on two factors:
• Temperature (maximum temperature above which the gas cannot be liquefied). Liquefactions
of gases depend on critical temperature. When the critical temperature is more the gases
will be liquefied and more adsorption occurs.
• Van der Waal’s forces: Easily liquefiable gases possess greater Vander Waal’s forces than
permanent gases, so they are adsorbed more readily.
(iv) Exothermic Nature
Heat of adsorption is defined as the energy liberated when 1 g mol of a gas is adsorbed on a
solid surface. Increase in temperature increases the kinetic energy of the gas molecules and
it results in more number of collisions of gas molecules over the adsorbent surface.
(v) Pressure
When pressure is increased then the rate of adsorption increases initially. The extent
of adsorption is expressed as x/m where ‘x’ is amount of adsorbate; ‘m’ is mass of
adsorbent when the dynamic equilibrium is established between free gas and the
adsorbed gas. But after some time it reaches appoint where no more adsorption
occurs and at this point adsorption is independent of pressure.
ADSORPTION OF SOLUTE FROM
SOLUTIONS
The process of adsorption of solutes on solid surface can take place from solutions.
For example the activated animal charcoal adsorbs colouring matter present in
sugar solution and clarifies the sugar solution. It also has the capacity to adsorb
acetic acid and oxalic acid from water thereby reducing the concentration of acids
in water.
There are two (or more) components present in a solution namely solute and solvent.
The solute may be present in the molecular or ionic form. The extent of adsorption
from solution depends upon the concentration of the solute in the solution, and
can be expressed by the Freundlich Isotherm.
FREUNDLICH ISOTHERM
The value of k depends upon the nature of solid, its particle size, temperature,
and the nature of solute and solvent etc. It the graph is plot between x/m
against c which gives a straight line which is similar to Freundlich adsorption
isotherm.
FACTORS AFFECTING ADSORPTION OF SOLUTES
FROM SOLUTION
Nature of adsorbent
Adsorption ofsolute from solution is highly specific. Adsorption depends mainly on
nature of adsorbent.
Temperature
Adsorption from solution decreases with rise in temperature.
Concentration of solute
Adsorption from solution decrease with decrease in concentration of solution.eg
charcoal adsorbs water from dilute KCl solution whereas charcoal adsorbs KCl from
concentrated KCl solution.
ADSORPTION ISOTHERM
The process of adsorption is usually
studied through graphs know as
adsorption isotherm. It is the graph
between the amounts of adsorbate (x)
adsorbed on the surface of adsorbent (m)
and pressure (P) at constant temperature.
FREUNDLICH ADSORPTION
ISOTHERM
At low pressure, extent of adsorption is directly proportional to pressure:
x/m ∝ p1
At high pressure, extent of adsorption is independent of pressure:
x/m ∝ p0
At intermediate value of pressure, adsorption is directly proportional to
pressure raised to power 1/n ⋅ n value is greater than 1.
x/m ∝ p(1/ n)
To remove proportionality a proportionality constant ‘k’ is used which is
known as adsorption constant and we get
x/m ∝ k.p(1/ n)
The above equation is known as Freundlich Adsorption equation.
PLOTTING OF FREUNDLICH ADSORPTION
ISOTHERM
Taking log both sides of equation, we get,
log x/m = log k + 1/n log P
The equation is comparable with equation of
straight line, y = m x + c where, m represents
slope of the line and c represents intercept on
y axis. Plotting a graph between log (x/m) and
log p, we will get a straight line with value of
slope equal to 1/n and log k as y-axis intercept.
LIMITATION OF FREUNDLICH ADSORPTION
ISOTHERM
1. Freundlich equation is purely empirical and has no
theoretical basis.
2. The equation is valid only upto a certain pressure and
invalid at higher pressure.
3. The constants k and n are not temperature independent,
they vary with temperature.
4. Frendilich’s adsorption isotherm fails when the
concentration of the adsorbate is very high.
L ANGMUIR ADSORPTION ISOTHERM
In 1916, Irving Langmuir proposed another adsorption
Isotherm which explained the variation of adsorption with
pressure
ASSUMPTIONS OF LANGMUIR ISOTHERM
Langmuir proposed his theory by making following assumptions.
(i) Surface is energetically uniform. Fixed number of vacant or adsorption sites are available
on the surface of the solid.
(ii) All the vacant sites are of equal size and shape on the surface of adsorbent. Each site
can hold maximum of one gaseous molecule and a constant amount of heat energy is
released.
(iii) Heat of adsorption is constant throughout the surface and it ranges from 0 to 1.
(iv) Dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules.
(v) Adsorption is monolayer or unilayer.
D E R I VAT I O N
Langmuir Equation depicts the relationship between the extent of adsorption and pressure.
Langmuir proposed that dynamic equilibrium exists between adsorbed gaseous molecules and the
free gaseous molecules. Using the equilibrium equation, equilibrium constant can be calculated.
Adsorption
A(g)+B(s) AB
Desorption
where A(g ) − is unadsorbed gaseous molecule
B(s) − is unoccupied metal surface and
AB − is adsorbed gaseous molecule
According to Kinetic theory,
• Rate of forward reaction = Ka [A] [B]
• Rate of backward reaction = Kd [AB]
• At equilibrium, Rate of forward reaction is equal to Rate of backward reaction
• Ka [A] [B] = Kd [AB]
• A new parameter ‘θ’ is introduced.
L A N G M U I R A D S O R P T I O N E Q U AT I O N .
LIMITATIONS OF L ANGMUIR ADSORPTION
EQUATION
(i) The adsorbed gas has to behave ideally in the vapour phase. Langmuir equation is valid
under low pressure only.
(ii) Langmuir Equation assumes that adsorption is monolayer. But, monolayer formation is
possible only under low pressure condition. Under high pressure condition the assumption
breaks down as gas molecules attract more and more molecules towards each other.
(iii) Another assumption is the surface of solid is homogeneous but in real solid surfaces is
heterogeneous.
(iv) Equation assumed molecules do not interact with each other.
(v) In adsorption liquefication of gases taking place, which results in decrease in
randomness but the value is not zero.
ADSORPTION THEORY
This theory was postulated by Faraday in 1833. It explains the action
of heterogenous cataylsis. Heterogenous catalysis has five steps.
KINETICS OF SURFACE REACTION
The kinetics of heterogeneously-catalyzed reactions might
vary with the partial pressures of the reactant gases above
the catalyst surface which can be predicted by using the
Langmuir isotherm.
KINETICS OF UNIMOLECUL AR
DECOMPOSITION
Examples of unimolecular decomposition
1. Decomposition of NH3 to N2 and H2 on metal surfaces,
2. Decomposition of Phosphine on glass,
3. Decomposition of Formic acid on glass, Pt, Ag, Au, or TiO2.
Consider the surface decomposition of a molecule A , i.e. the
process
A(g) ⎯⎯→ A (adsorbed) ⎯⎯→ Product
Assumption
1. The decomposition reaction occurs uniformly across the surface sites.
Molecule ‘A’ may be
adsorbed and is not restricted to a limited number of specific sites.
2. The products are very weakly bound to the surface and, they can be easily
deformed.
3. The rate determining step is the surface decomposition step.
According to Langmuir adsorption isotherm molecule ‘A’ adsorbed on the
surface is in
equilibrium with the gas phase and the surface concentration is represented
as:
KINETICS OF BIMOLECUL AR REACTION
(L ANGMUIR-HINSHELWOOD)
Between molecular adsorbates.
Consider the reaction:
A(g) ←⎯→ A(ads)
B( g) ←⎯→ B(ads)
A(ads) + B(ads) -rds→ AB(ads) ⎯f⎯ast⎯→ AB(g)
TYPES OF ADSORPTION ISOTHERM
Adsorption process is usually studied
through graphs known as adsorption
isotherm. After saturation pressure Ps,
adsorption does not occur anymore, as
there are limited numbers of vacancies on
the surface of the adsorbent. At high
pressure when all the sites are occupied
and further increase in pressure does not
cause any difference in adsorption process.
At high pressure, adsorption is independent
of pressure. There are 5 different types of
adsorption isotherms and each of them has
specific characteristics.
TYPE I ADSORPTION ISOTHERM
Type I Adsorption isotherm is for very
small pores or microporous
adsorbents. Adsorption occurs by
filling of micropores and it mainly
depicts Monolayer adsorption. Eg.
Adsorption of Nitrogen or Hydrogen
on charcoal around −1800°C.
TYPE II ADSORPTION ISOTHERM
Type II Adsorption isotherm shows large deviation from
Langmuir model of adsorption. They are most
frequently encountered when adsorption occurs on
nonporous powders or macro-porous adsorbents
with unrestricted monolayer -multilayer adsorption.
The intermediate flat region in the isotherm
corresponds to monolater formation. When the
monolayer formation of the absorbed molecules are
complete, multilayer formation take place
corresponding to the ‘sharp knee’ of the isotherms.
Eg: Iron (Fe) catalyst and Nitrogen (N (g)) adsorbed
at −1950°C on silica gel.
TYPE III ADSORPTION ISOTHERM
Type III Adsorption Isotherm also shows
large deviation from Langmuir
model. This isotherm explains the
formation of multilayer. They are
characterized principally by heats of
adsorption which are less than the
adsorbate heat of liquefaction.
Eg: Bromine (Br2) at 790°C on silica
gel or Iodine (I2) at 790°C on silica
gel.
TYPE IV ADSORPTION ISOTHERM
Type IV Adsorption Isotherm occur on porous adsorbents
possessing pores in the range of approximately 15-
1000 angstroms (A). At lower pressure region of
graph is quite similar to Type II. This explains
formation of monolayer followed by multilayer.
The intermediate flat region in the isotherm
corresponds to monolayer formation.
The saturation level reaches at a pressure below the
saturation vapor pressure. This can be explained on
the basis of a possibility of gases getting condensed
in the tiny capillary pores of adsorbent at pressure
below the saturation pressure (PS) of the gas.
Eg. Adsorption of Benzene on Iron Oxide (Fe2O3) at
500°C and adsorption of Benzene on silica gel at
500°C.
TYPE V ADSORPTION ISOTHERM
Type V Adsorption Isotherm results from
small adsorbate-adsorbent interaction
potentials similar to the Type III isotherms.
However, Type V isotherms are also
associated with pores in the same range
as those of the Type IV isotherms.
Eg: Adsorption of Water (vapors) at
1000°C on charcoal.
APPLICATIONS OF ADSORPTION
•
CATALYSIS
INTRODUCTION
DEFINITION
The process by which a substance
speeds up a chemical reaction
without being consumed or altered
in the process.
CATALYSIS CYCLE
TERMS
MECHANISM OF CATALYTIC
REACTION
CRITERIA OR CHARACTERISTICS OF
A CATALYST
(vi) A catalyst should remain unchanged in mass and chemical
composition during end of the reaction.
(vii) Catalyst can alter only the speed of the reaction but it should
not affect the equilibrium of the reaction.
(viii) Catalysts are more active at its optimum temperature.
Change of temperature alters the rate of a catalytic reaction as it
would do for the same reaction without a catalyst.
(ix) The catalytic activity can be altered by adding a small amount
of foreign substance. Such substances which catalyse the catalyst
are called as promoters and the substance which inhibits the
reaction are called as catalytic poisons or anti-catalyst.
TYPES OF CATALYSIS
Heterogene
Homogeneo
ous
us catalysis
catalysis
AUTOCATALYSIS
CATALYTIC POISONING AND
PROMOTERS
CATALYTIC POISONS
Small amounts of substances can reduce the activity of
catalyst. If the reduction in activity is reversible, the
substances are called inhibitors. Inhibitors are sometimes
used to increase the selectivity of a catalyst by retarding
undesirable reactions.
A substance which destroys the activity of the catalyst to
accelerate a reaction is called a poison and the process is
called Catalytic Poisoning.
Types of Catalytic Poison
(i) Temporary Poisoning
Catalyst regains its activity when the poison is removed
from the reaction
(ii) Permanent Poisoning
a. Catalyst cannot regain its activity even if the catalytic
poison is removed.
b. Eg.AS2O3 poisons catalyst Pt permanently in
manufacturing of SO3.
ACID AND BASE CATALYSIS
A number of homogeneous catalytic reactions are known which are
catalysed by acids or bases, or both acids and bases. These are often
referred to as Acid-Base catalysts.
Arrhenius pointed out that acid catalysis was, in fact, brought
about by H+ ions supplied by strong acids, while base catalysis
was caused by OH– ions supplied by strong bases.
HOMOGENEOUS CATALYTIC REACTION AND
HETEROGENEOUS CATALYTIC REACTION
1. Phase
a. Homogeneous: Liquid.
When a reactant is in the gas form such as in hydrogenation, what reacts is
actually the gas dissolved in the liquid phase, and not the one in the gas phase.
b. Heterogeneous: Liquid, Gas, Solid
2. Operative Temperature
c. Homogeneous: Generally low temperatures.
The presence of a solvent, which needs to dissolve the catalyst, might limit the
temperature of the reaction.
d. Heterogeneous: The only limitation is the stability of the catalyst under harsh
conditions.
BIOLOGICAL CATALYST - ENZYMES
MECHANISM OF ENZYME CATALYSIS
CHARACTERISTICS OF ENZYME
CATALYSIS
FACTORS AFFECTING ENZYME ACTIVITY
TERMINOLOGIES IN MATERIAL PREPARATION
Precursor - In chemistry, a precursor is a compound that participates in the chemical
reaction that produces another compound. In biochemistry, the term "precursor" is used
more specifically to refer to a chemical compound preceding another in a metabolic pathway.
Calcination - Calcination (also referred to as calcining) is a thermal treatment process
applied to ores and other solid materials in order to bring about a thermal
decomposition, phase transition, or removal of a volatile fraction. The calcination process
normally takes place at temperatures below the melting point of the product materials.
Calcination is to be distinguished from roasting, in which more complex gas-solid reactions
take place between the furnace atmosphere and the solids, however calcination takes place
in the absence of air.
Ageing - Catalyst aging is the loss of catalytic activity over time.
Agglomeration - Agglomeration is the process by which particles adhere to one another to
create larger aggregates. These aggregate particles are held together by a variety of
relatively weak physical and chemical forces depending on adhesion methodology.
Regeneration - Regeneration is a process to restore the catalytic activity of a spent catalyst.
It normally involves thermal treatment to remove surface coatings and/or absorbed species.
Types – continuous catalyst regeneration (CCR)
APPLICATIONS OF CATALYSIS
• Catalytic converters
• Petroleum Refining
• Chemicals and petrochemicals
• Other
(i) Fischer-Tropsch and Coal gasification processes for producing
synthetic fuel gases and liquid fuels
(ii) Various processes for producing many different medicine
ASSIGNMENT
1. What is adsorption. Mention factors affecting the extent of adsorption.
2. Note down difference between chemisorption and physisorption.
3. Describe in brief: (a) Catalytic poisons (b) Acid-base catalysis (c) Autocatalysis
4. Explain adsorption theory.
5. Note down Freundlich’s adsorption isotherm for liquid and gases as adsorbate
6. Derive Langmuir’s equation.
7. What is adsorption isotherm? Explain its types and specific characteristics.
8. Note down the characteristics of enzyme catalysis and factors affecting the
enzyme activity in catalysis.
9. What is catalytic poisoning? How does promoter affect catalysts?
10.Explain kinetics of surface reaction.
11.Note down applications of adsorption and catalysis process.
12.Explain different types of catalysis.
